Electronic Supplementary Material (ESI) for Green Chemistry.

This journal is © The Royal Society of Chemistry 2019

Supporting Information

One-pot Conversion of Lysine to Caprolactam over Ir/H-Beta Catalysts

Joby Sebastian, Mingyuan Zheng*, Yu Jiang, Yu Zhao, Hua Wang, Zhendong Song,
Xinsheng Li, Jifeng Pang and Tao Zhang*

Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P.R.
China. E-mail: myzheng@dicp.ac.cn; taozhang@dicp.ac.cn.

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Experimental section
Materials: The zeolites (HB-124, HB-80, HB-50, HY-10, ZSM-5 (42)) were purchased
from Nankai University Catalyst Co. Ltd., acidic Al2O3, anatase TiO2, CeO2, MoS2,
Nb2O5, La2O3 and Activated carbon were all commercial. The precursors for noble and
non-metals are 21.06 wt% H2IrCl6 solution in H2O, RhCl3.xH2O, HAuCl4.xH2O, RuCl3,
H2PtCl6.6H2O, PdCl2, HReO4 and Ni(NO3)2.6H2O.
Reagents: L-lysine, α-amino-ε-caprolactam (L and DL- ACPL) hydrochloride, anhydrous
MeOH (H2O < 0.05%), THF, ethanol, 1,2-propanediol, γ-valerolactone, 37% HCHO
solution. All the reagents were used as received.
Catalyst synthesis: All the catalysts were prepared by the incipient wetness
impregnation method. A typical synthesis of 2Ir/HB-124 as follows, first the support was
dried at 550oC for 6 hours. To 1.0 g of the dried support, 0.095 mL of H2IrCl6 precursor
solution (21.06 wt% of Ir) along with 1.5 mL of deionized H2O was added. It was then
mixed well, covered and kept at room temperature for 6 hours followed by drying at 80oC
for 12 hours. It was then ground and calcined at 550oC (2oC/min) for 4 hours. The
catalyst was used for the experiments without any pretreatments. The same procedure
was followed for other supports like Al2O3, TiO2, CeO2 and AC. The calcination step was
avoided for AC.
Catalysts with other metals such as Rh, Pt, Ru, Au, Pd, Re and Ni were also prepared
following the above procedure. These catalysts were reduced at a temperature of 300oC
for Rh, Ru, Pd, Au, 350oC for Pt, 400oC for Ir/AC, 450oC for Ni and 500oC for Re for 3
hours (3oC/min) and then passivated in the O2/N2 mixture for 4 hours.
One-pot conversion of L-lysine to CPL: The reaction was performed in a high-pressure
Parr-4848 Hastelloy autoclave (100 mL) equipped with a mechanical stirrer and an
automatic temperature control system. The reactor was first charged with 0.200 g of L-
lysine and 0.100 g of 2Ir/HB-124 catalyst. A volume of 20 mL of anhydrous methanol
was then introduced. Then the reactor was purged with H2 (10 bar) for at least five times
and pressurized to 20 bar. The reactor temperature was slowly increased to 240oC
(2.2oC/min) and maintained for a period of 6 hours. At the end of the reaction time, the
reactor was cooled down to room temperature. It was then depressurized, the product
mixture was filtered and analyzed by HPLC and GC. Recycle experiments were

2
conducted as follows; after the reaction, the catalyst was separated by filtration and used
for the next run without any pretreatments like drying or calcination.

ACPL to CPL: About 0.050 g of L-ACPL.HCl was charged into the reactor along with
0.025 g of 2Ir/HB-124 and 20 mL of anhydrous methanol. The reactor was purged with
H2 (10 bar) at least five times and pressurized to 20 bar. The temperature was slowly
increased to 250oC (2oC/min) and maintained for a period of 1 hour. At the end of the
reaction time, the reactor was cooled down, depressurized, filtered and analyzed by
HPLC and GC.

DMAC to CPL: About 0.050 g of DMAC was introduced to the reactor along with 0.025
g of 2Ir/HB-124 and 20 mL of anhydrous methanol. It was then purged with H2 and
pressurized to 20 bar. The temperature was set to 250oC (2oC/min) and the reaction time
to 1 hour. At the end of the reaction time, the reactor was cooled down, depressurized, the
product was filtered and analyzed by GC. Recycle experiments were conducted as
follows; after the reaction, the catalyst was separated by filtration and used for the next
run without any pretreatments like drying or calcination.
Fixed-bed reactions of DMAC to CPL: The reactions were carried out in a stainless
steel tube reactor (6 mm i.d. and 31 cm length). 2Ir/HB-124 was sieved into a 20-40
mesh size and loaded (0.30 g) into the reactor. The reactor was heated to 250oC (2oC/min)
under a H2 flow of 50 mL/min. The hydrogen pressure in the reactor was maintained at
65 bar throughout the reaction and the flow was maintained at 50 mL/min. A 0.25 wt% of
DMAC in anhydrous methanol was used as the feed (0.5 mL/min, WHSV = 100).
Product samples were collected at regular time intervals and were analyzed by GC.
Synthesis of DMAC: About 1.0 g of L-ACPL.HCl, 0.720 g of 5Pd/AC, 1.7 mL of 37%
HCHO and 20 mL of anhydrous methanol were charged into the reactor. The reactor was
then flushed five times with 10 bar H2 and pressurized to 40 bar. The reactor temperature
was set to 50oC and time to 4 hours. In the end, the reactor was cooled down to room
temperature and depressurized. The solvent methanol and unreacted HCHO were
removed by rota-evaporation and the solid product obtained was double recrystallized
from methanol-ethyl acetate mixtures. The final product, DMAC was obtained through
decantation and drying at 60oC overnight. The purity of the product was analyzed by 1H

3
& 13C NMR spectroscopy (Figure S4). It was found that the purity of DMAC as-
prepared is >98%.

Product analysis: L-lysine and L-ACPL conversions were analyzed by using an HPLC
instrument (Column: ACE Excel 5 AQ, 250 x 4.6 mm id, UV-detector 210 nm, 35oC,
solvent A = H2O containing 10 mmol of HCOONH4, solvent B = 90% CH3CN and 10%
H2O, flow = 0.6 mL of 80% A & 20% B). DMAC conversion and CPL yield were
quantified using a GC instrument fitted with an FFAP column (30m x 0.32 mm).
Identification of the products was done using a GC-MS instrument fitted with a DB-5
column (30 m x 0.25 mm x 0.25 μm). The conversion, yield and selectivity of different
compounds were calculated using the following equations with the calibrated values
(benzyl alcohol as the standard).

𝐼𝑛𝑝𝑢𝑡 𝑙𝑦𝑠𝑖𝑛𝑒 (𝑚𝑜𝑙) ‒ 𝑂𝑢𝑡𝑝𝑢𝑡 𝑙𝑦𝑠𝑖𝑛𝑒(𝑚𝑜𝑙)

𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 (%) = × 100
𝐼𝑛𝑝𝑢𝑡 𝑙𝑦𝑠𝑖𝑛𝑒 (𝑚𝑜𝑙)

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑃𝐿 ( 𝑜𝑟 𝐷𝑀𝐴𝐶)

𝑃𝑟𝑜𝑑𝑢𝑐𝑡 𝑦𝑖𝑒𝑙𝑑 (%) = × 100
𝐼𝑛𝑝𝑢𝑡 𝑙𝑦𝑠𝑖𝑛𝑒 (𝑚𝑜𝑙)

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑃𝐿
𝐶𝑃𝐿 𝑠𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 (%) = × 100
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐷𝑀𝐴𝐶 𝑐𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑

Nitrogen balance of the reaction: The amount of nitrogen in the reaction can be
partially balanced to DMAC formation. On the other hand, dimethylamine and
trimethylamine15 might be formed via C-N(CH3)2 bond hydrogenolysis of DMAC
in methanol, and will contribute to the nitrogen balance. Figure S5 shows the GC-
MS spectra of the product mixture. Notable amount of trimethylamine was found
in the products but without dimethylamine observation. Because of the high
volatility and the difficulty in the accurate quantification, the byproduct
trimethylamine was not quantified. Thus, it can be confirmed that besides DMAC,
trimethylamine is the major co-product which contributes to the nitrogen balance.

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The molecular dimensions of L-lysine, ACPL, DMAC and CPL were calculated using
Materials Studio software.

ICP-OES analysis: The amount of Ir leached in to the product mixture was analyzed on
a PerkinElmer ICP-OES 7300DV instrument after removing the organic phase.

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Table S1: Effect of solvent on CPL production from L-lysine and DMAC.
Solvent CPL yield (mol%)

Methanol 23.0
Ethanol 2.8
Tetrahydrofuran --
1,2-Propanediol --
γ-valerolactone --
H2O --
Methanol + H2Oa 13.8
Ethanolb <1
Tetrahydofuranb <1

Reaction conditions: L-lysine = 0.200g, 2Ir/HB-124 =

0.100g, solvent = 20 mL, PH2 = 30 bar, T = 240oC, t = 6 h.
aMeOH = 19.5 mL and H O = 0.5 mL, t = 4 h. bDMAC as
2
the feedstock.

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 30

24

Yield (C%) 18
CPL
DMAC

12

8 12 16 20 24
Pressure (bar)
Figure S1: Effect of reaction pressure on DMAC and CPL yield. Reaction conditions:
L-lysine = 0.200g, 2Ir/HB-124 = 0.100g, MeOH = 20 mL, T = 250oC, t = 4 h.

30

20
Yield (C%)

CPL
DMAC

10

0
0.04 0.08 0.12 0.16 0.20
Catalyst quantity(g)

Figure S2: Effect of catalyst quantity on DMAC and CPL yield. Reaction conditions: L-
lysine = 0.200g, MeOH = 20 mL, T = 250oC, PH2 = 20 bar, t = 4 h.

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 NH2
N
H O
ACPL

O
H2N CH3OH
N Unknown
OH + N + byproducts
NH2 H2 N N
H O H O
Lysine DMAC CPL

O
H2N
OH
N
H O

Figure S3: Summary of the L-lysine to CPL reaction route observed over Ir/HB-124
catalysts.

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Figure S4: 1H and 13C-NMR spectra of purified DMAC in D2O synthesized from L-
ACPL.HCl.

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Figure S5: GC-MS spectra of product mixture showing the presence of trimethylamine.
Reaction conditions: L-lysine = 0.200g, 2Ir/HB-124 = 0.100 g, MeOH = 20 mL, PH2 = 30
bar, T = 240 oC, t = 6 h.

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